IMPROVED MOLTEN METAL DECOMPOSITION APPARATUS AND PROCESS

Abstract: In an improved molten metal hydrogen generation bath, baffles form a draft tube or chimney-effect near the center of the bath. Flow through the chimney is aided by maintaining a temperature differential favoring convection and, optionally, a differential pressure between the portions of the bath on either side of the baffle-chimney arrangement. Feed is added to the feed zone and oxygen is added to the oxidation zone, emitting H2 from the feed zone and CO from the oxidation zone. Baffles may be made simply of brick work or high temperature metal and can fit into existing refractory-lined molten metal vessels. Products can be mixed as syngas feed for Fischer-Tropsch synthesis. Additionally, the Boudouard endothermic reaction (CO2 + C } 2CO) can be used to control temperatures by injecting CO in place of oxygen.

Description: IMPROVED MOLTEN METAL DECOMPOSITION APPARATUS AND PROCESS This application is a continuation-in-part application of USSN 5 07/930,250 filed 08/13/92. Cross Reference to Related Applications U.S. Patent application 542, 234, filed June 21, 1990; 625,350, filed December 11, 1990; 838,642, filed February 20, 1992; and 763,097, filed 10 September 20, 1991; all relate to the general field of the present invention. Background of the Invention 1. Field of the Invention: 15 The present invention relates to the general field of molten baths for the disassociation of material containing carbon, and preferably hydrogen as well, generally classified in U.S. Patent Office, Class/Subclass: 60/39.12, 48/195, and 23/230A. 20 2. Description of the Prior Art: U.S. 4,187,672 and U.S. 4,244,180 to Rasor feed a mass of carbonaceous fuel; e.g., coal, into a high temperature liquid; e.g., molten iron, at a temperature high enough to carbonize the feed; e.g., near 2850° F (1565° C) and introduces air or other oxygen source into the 25 reactor to react with carbon dissolved in the liquid and uses the hot fuel \ gas to produce useful energy. WO 9Z/01492 to Nagel teaches two immiscible zones (layers) of different molten metal temperatures. Mayes U.S. 4,338,096 teaches methods for controlling the flow of molten-mass reaction medium into a reaction zone by utilizing a gas-lift effect on the molten medium and apportioning the flow of control gas to the desired flow of molten medium. Mayes does not suggest movement of liquid from one zone to another by means of convection. Bach U.S. 4,574,714, and U.S. 4,602,574 do not suggest the plural zones of the present invention with organic feed introduced into one zone and oxidizer introduced into a second zone, and with the vapor phases and liquid phases of the two zones being separated by barriers as in the present invention. TyrerU.S. 1,803,221 teaches production of hydrogen from methane in a two-zone unit, but provides no means for flow by convection between the two zones and does not suggest the specialized baffle separators of the present invention. Axelsson U.S. 4,511,372 does his whole process in a single vessel at high pressure, primarily to suppress dust. The lance of the present invention can be distinguished from the conventional tuyeres commonly used in steel making, in that the tuyeres are submerged into the molten steel and do not pass through any substantial portion of the molten steel. Further, the tuyeres are generally used for introducing oxygen, argon, and other gases, whereas the present lances are particularly used for introducing feed materials which contain hydrocarbons which can cause substantial coking. Therefore, it is a particular objective of the present invention to substantially reduce the amount of coking formed within the conduit or lance of the invention. This reduces the plugging difficulty which is often encountered with lances operating at these high temperatures, particularly when the lances are injecting liquids comprising hydrocarbons. Summary of the Invention 1. General Statement of the Invention: Referring to Figure 1, according to the invention, a vessel having top and bottom walls a feed zone and an oxidizing zone and containing a molten bath to levels 116, 118 respectively for the decomposition of carbon- (and preferably hydrogen-) containing materials is improved by providing upwardly extending submerged baffle means 114 above the bottom wall abutting the feed zone and defining one wall of a recycle zone (chimney) 108 communicating between liquid in the oxidizing zone and in the feed zone. The invention also comprises horizontal extending baffle means 115 above the bottom wall. The horizontally extending submerged baffle means 115 is integral with a lower portion of the downwardly extending baffle means 114 and arranged so as to define the lower end of a generally L-shaped recycle zone 108, much as a hearth is arranged beneath a chimney. The invention further comprises vapor zone separator or baffle means 112, the vapor zone separator means separates the vapor space above the liquid baths so that the vapor space of the feed zone is separated from the vapor space of the oxidizing zone. This vapor zone separator means 112 abuts the oxidizing zone and extends downward into the liquid of the oxidizing zone to define the other wall of said chimney of the recycle zone 108, but not sufficiently far so as to contact the horizontal extending baffle means 115. Apparatus: Closed vessel 100: The vessel includes a top wall 100A and a bottom wall 100B and is preferably lined with brick or castable refractories and may be pre-stressed to maintain the refractories in compression even when the vessel is pressurized and hot. Downwardly extending baffle means 114 and horizontal extending baffle means 115 can be made of refractory materials or even of tungsten, tantalum, or other high-melting refractory metal which may be coated with refractory ceramics. Vapor zone separator means 112 will preferably be of the same material as downwardly extending baffle means 114, and will preferably be hermetically attached to the top wall of closed vessel 100. Oxidizer feed means 107 can be any suitable, tuyere design, well-known in the steel-making industry. Feed inlet 105 can operate by gravity or pump (high pressure pump if the vessel operates under pressure). Fischer-Tropsch Synthesis The preferred CO and H 2 products are useful for the conventional Fischer-Tropsch synthesis taught e.g., in Chemical Process Industries by R. Norris Schreve, McGraw-Hill, 1967, p. 775. Boudouard Reaction: This reaction, discussed in U.S. 4,412,914, 4,450,241, 4,869,879, and 4,915,820 all to W. P. Hettinger et al, reacts injected C0 2 with carbon in the molten metal to form 2CO and cool the melt as desired. Metal: While iron is most preferred for specialized applications, copper, zinc, especially chromium, manganese, or nickel, or other meltable metal in which carbon is somewhat soluble, may be used alone or in mixture. Feed Materials: Natural gas (CH 4 ), liquified petroleum gas (LPG), propane, petroleum naphtha, light or heavy distillate, vacuum and other resids, solvent de-asphalted pitch (SDA), aromatic extracts, FCC slurry oil; trash garbage, tires, coal and virtually any other hydrocarbon-containing material. Products: Products are CO, CO,, H 2 plus sulfur and other contaminants in feed which may be outputted in slag which can be periodically drained off. In refineries, sulfur is preferably outputted as gas in the hydrogen stream and is then treated conventionally by the Claus process and the SCOT (Shell Claus Offgas Treatment) unit. Controls: Conventional analog or digital controls are used, measuring temperature, preferably with optical or infrared pyrometer or protected thermocouple; carbon by spectrometer; level by nuclear radiation and admitting feed, CH 3 , C0 2 , H 2 0 to maintain temperature, which must, of course, be high enough (e.g., at least 1,250° C in feed zone, 1,300° C in oxidizing zone) to maintain the particular metal carbon composition liquid and dissolved carbon level and H 2 production within preset limits. Temperature is preferably 1,150° to 1,600°, more preferably 1,250° to 1,500° , and most preferably 1,300° to 1,450° C in the feed zone, and usually preferably 50° to 150° C higher in the oxidation zone. Batch/Continuous Operation: While the Examples describe the invention on a continuous basis, it may, of course, be practiced on a batch or semi-batch basis with discontinuous flows of starting materials into the molten-metal vessel and with intermittent withdrawal of slag and/or product gases. Flexibility: Wide ranges of feed rate, feed composition, and contaminants can be accommodated, even wide swings over short time intervals. 2. Utility of the Invention: The present invention is useful for the production of a wide variety of end-products, including all those which can be produced by the well-known Fischer-Tropsch process, e.g., naphthas, diesel fuel, jet fuel (kerosene), as particularly commercialized by Sasol in South Africa. The Mobil Oil "M-Gas" process (U.S. 3,998,899, etc.) may be employed. At the present time, the invention will be particularly valuable for the flexible production of reformulated fuels as mandated or as desirable for protection of the environment, e.g., methanol, methyl tertbutyl ether (MTBE) and tert amyl ether (TAME), etc. In its preferred embodiments, the invention functions entirely from distress or low-valued hydrocarbons, air (for oxidation), and water (to supply hydrogen and additional oxygen). It is particularly noteworthy that the invention can utilize the exothermic carbon oxidation reaction so that it can function without need for external energy input. Additionally, the endothermic Boudouard reaction (C0 2 + C - 2CO) can be used to control temperature within the two reaction zones, and particularly to control the differentials so as to adjust convection circulation of materials between the zones as desired. Syngas uses, per Kirk-Othmer, CO/H, without any other reactants as building blocks, e.g., glycol synthesis, modified Fischer-Tropsch syntheses to olefins or waxes, and acetic acid synthesis; those involving CO/H 2 and employed to make additional use of compounds derived from synthesis gas, e.g., homologation of methanol to ethanol; those that use a deravative based on CO/H 2 , e.g., methanol, as a starting material for a further reaction sequence, e.g., Mobil's MTG (methanol to gasoline) process or the vinyl acetate process; and energy-efficient processes, e.g., those that make syngas for use in combined-cycle plants; and those that use the carbon monoxide for subsequent syntheses, e.g., of acetic anhydride, acrylates, Koch acids, etc. Brief Description of the Figures Figure 1 is a schematic diagram of a section view of the closed vessel 100 showing the feed zone 104 and the oxidizing zone 106 separated by the chimney/hearth-like recycle zone 108 defined by downwardly extending baffle means 114/horizontal extending baffle means 115 and vapor zone separator means 112, along with the vessel 100. Figure 2 is a detail of Figure 1 showing the baffles 135 and 136. Figure 3 is a schematic diagram showing the optional water-gas shift reactor 60, Fisher-Tropsch reactor 64, the optional Boudouard reactor 80 which occurs in the molten bath oxidizing zone 106, and the removal of carbon dioxide by means of the Benfield or Pressure Swing Absorption processes. Figure 4 shows a preferred lance, with the lance in place as element 205 impinging on the surface of the liquid so as to depress it and actually pierce it, forming bubbles. Figure 5 is a schematic of a more preferred lance. Figure 5A is a cross sectional area at section AA of the lance, and Figure 5B is a cross-sectional detail of the lance tip. Figure 6 is a schematic of a slanted lance which may be above the molten surface or can preferably extend into the molten bath. Description of the Preferred Embodiments Referring to Figure 1, the main vessel (a refractory-lined steel vessel 100) encloses and partially defines feed zone 104, oxidizing zone 106, lower circulation zone 113, and L-shaped recycle zone 108. Feed zone 104 receives feed through feed inlet 105. Oxygen enters through oxidizer feed means 107 into oxidizing zone 106. Oxidizing zone 106 and recycle zone 108 are controlled by pressure control means 120 which acts on control valve 128 and control valve 129 to throttle H2 outlet 130 and CO outlet 132 differentially as desired. Cooler 127 and cooler 126 protect control valve 128 and control valve 129 by cooling the products. Level controllers 133 and level controller 134 control the level in the feed and in the oxidizing zone, respectively, and feed signals to pressure control means 120 to maintain those levels. As shown schematically in Figures 4 and 6, the feed 105 will preferably be directed downwardly with sufficient force to pierce the surface (or penetrate through a portion of the depth) of the molten metal bath 104, more preferably with sufficient force to cause bubbling and mixing of the feed with the liquid metal bath, and most preferably will extend below the molten surface. Figure 4 shows a preferred lance and shows the lance in place as element 205 impinging on the surface of the liquid so as to depress it and actually pierce it, forming bubbles. Figure 5 is a schematic of a more preferred lance. Figure 5A is a cross sectional area at section AA of the lance, and Figure 6B is a cross- sectional detail of the lance tip. Figure 2 is a detail of the baffles. Baffle 135 and baffle 136 are shown in more detail in Figure 2. Note that baffle 135 has both a horizontal and a vertical projection, whereas baffle 136 is primarily vertical in its projection and is sealed hermetically to the edges of refractory-lined steel vessel 100 to effectively separate the gas spaces above the feed zone and the oxidizing zone. Together, baffle 135 and baffle 136 define lower circulation zone 113, recycle zone 108, and additionally separate the two gas phases as mentioned above. The recycle zone 108 is particularly formed by a hearth-like substantially horizontal projection of baffle 135 and the vertical projection of baffle 135 acts with baffle 136 to form a chimney-like vertical section to the recycle zone 108. This configuration is an important feature of the invention because it provides the necessary circulation which moves the carbon first through lower circulation zone 113 from the feed zone to the oxidizing zone 106 after feed zone 104, thence through recycle zone 108 after the carbon has been largely removed in the oxidizing zone closed vessel 100. In operation, the apparatus of Figure 1 has a temperature of approximately 1300° C in feed zone 104, 400°C in oxidizing zone 106, and emits hydrogen and CO at approximately those temperatures, respectively. Pressure within closed vessel 100 is preferably from 0 to 50 bars, more preferably from 0.1 to 40 bars, and most preferably from 1 to 25 bars above atmospheric, though higher pressures, even as high as 100 bars can be utilized with special construction if desired for special circumstances. The feed will generally be fed from a source at ambient temperature, or in any case at much lower temperature than the temperature of the molten bath. Generally, keeping the feed material as cool as possible as it approaches the high temperature of the bath will be desirable to avoid coking within the feed lance. This will generally be accomplished by maintaining a velocity within the conduit in the range of from about 1-10 meters per second, and sizing the conduit so the residence time of said feed material in said conduit is from about 0.1-10 seconds. In general, this will keep the temperature in the conduit through which the feed material is flowing below about 315° C (about 600° F), more preferably below about 200° C (below about 400° F). Feed zone 104, preferably contains about 0 to 4.3%, more preferably about 1 to 4%, and most preferably 3% carbon. The carbon content in oxidizing zone 106 is an amount less than in feed zone 104 determined by the circulation rate of the molten metal and the feed rate of carbon to the feed zone. The vessel is a conventional refractory-lined design of steel suitable for the temperature and other surface conditions. The oxygen source is preferably 99.9% oxygen distilled from an oxygen plant operating on air (not shown) but may be air where the additional nitrogen is tolerable. Referring now to Figure 4, lance 205 is shown entering through the upper portion of vessel 100 and is directed downwardly toward, or preferably extending below the liquid surface of molten bath 104, ending in communication with nozzle 206 which forms a jet 210 of fluid directed downwardly toward the surface of molten bath 100 so as to depress the surface. Preferred embodiments would be feed materials flowing through conduit 205 will have sufficient velocity to actually penetrate below the surface of bath 104 to a depth of 3-100 cm (1-36 inches) below the nozzle tip and cause bubbling, and to reduce coke formation in the conduit. This can be achieved by using a nozzle 206 sufficiently small, as compared to the quantity of feed material fed to the conduit 205, to provide a velocity of the feed material leaving the nozzle in the range of from about 30-300, more preferably about 80-250, and most preferably about 100-200 meters per second (about 100 to 1000, more preferably 250 to 820, and most preferably 325 to 660 feet per second). It is also desirable to feed liquid feed material through the conduit 205 under a sufficient pressure to prevent the feed material from vaporizing in the conduit which can cause two-phase sputtering and reduce the flow capacity of the conduit 205. The conduit 205 is preferably jacketed with a jacket 212, preferably coaxially (concentric) with the conduit 205. Still more preferably, the conduit (lance) 205 can be surrounded by insulation shown in Figure 5B as surrounding the jacket to reduce quantities of coolant required to maintain the temperature in the conduit below a minimum temperature to avoid decomposition and/or vaporization in the conduit. Preferred insulation materials are magnesium oxide or aluminum oxide (alumina) powder or fibers, spinels (mixtures of magnesium oxide and aluminum oxide); preferred materials for the conduit itself are refractory metals, e.g. tantalum, and superalloys such as Inconel™ 625; and preferred materials for the jacket are silicon nitride, alumina, and boron nitride; preferred coolant materials to flow through the annular space 215 include argon, steam, and methane. In a particularly preferred design shown in Figure 5B, the coolant material itself is ejected axially around the feed material being ejected from nozzle 206 through openings 218, so that the coolant substantially surrounds the feed material exiting from the nozzle and directed toward the surface of the molten bath. Note that the conduit need not be entirely vertical, it may be slanted or bent or curved so as to provide a horizontal component to the jet 210 impinging on (or below) the surface of the molten bath, as shown in Figure 6. This horizontal component can be valuable in enhancing the circulation of the molten metal from the oxidizing zone to the oxidizing zone by flowing under baffle 135. Figure 6 shows a slanted conduit and jacket assembly (similar to that shown in detail in Figures 5, 5A, and 5B), but slanted so as to direct some of its force in a horizontal direction and cause fluid from molten bath 104 to more quickly circulate under baffle 135. (The conduit can also be slanted toward one side of the molten bath so as to cause circulation along one wall of the molten bath, and the baffle 135 can provide a larger lower opening at the point struck by flow from the lance, to further enhance circulation.) Various feeds are described under the following examples. EXAMPLES Example I Invention Operating on Solvent De-asphalted Bottoms (SDA) The feed rate is 22.3 tonnes/hour of SDA bottoms. The molten iron circulation is 9,000 tonnes/hour through recycle zone 108 and 1.75 tonnes/hour of hydrogen are emitted through H 2 outlet 130 and 43.8 tonnes/hour of CO are emitted through CO outlet 132. The results for this and other Examples are shown in Table A. Example II Invention with Methane Heat Balance The procedure of Example 1 is followed except that methane is added to the feed for heat balance. The ratio of hydrogen to carbon monoxide in the product gas is approximately 1 :1 on a molar basis. Example III Invention With Steam Heat Balance The procedure of Example I is followed, except that steam is added to the feed for heat balance. The ratio of hydrogen to carbon monoxide in the product gas is approximately 1:1 on a molar basis. Example IV Invention With Carbon Dioxide Heat Balance The procedure of Example I is followed, except that carbon dioxide is added to the feed for heat balance. The ratio of hydrogen to carbon monoxide in the product gas is approximately 1:3 on a molar basis. Example V Coal Feed to Invention The procedures of Example I are followed except that the feed is coal and the approximate molar ratio of carbon monoxide to hydrogen is 3:1 and except that 44,000 pounds/hour (20,000 Kg/hour) of steam are injected through oxidizer feed means 107 along with 22,500 pounds/hour of oxygen. Example VI Trash Fed to Invention The procedures of Example I are followed except that the feed is mixed non-metallic trash (largely waste paper) and garbage (largely organic food residue), which is dried by using heat from the process, and the molar ratio of carbon monoxide to hydrogen is approximately 1 :1. Example VII Methylene Chloride Disposal and Other Chlorinated Organics The procedure of Example 1 is followed except that the feed is methylene chloride, which has been contaminated and has no commercial value but represents a substantial disposal problem. Carbon monoxide and hydrogen are produced in a molar ratio of approximately 1 :1.5. To neutralize the chlorine and avoid toxic emissions, 2 pounds of slaked lime CaO per pound of methylene chloride is added near the top surface of feed zone liquid level 116 and oxidizing zone liquid level 118, and 2.5 pounds of slag per pound of methylene chloride is permitted to flow outward through an outlet (not shown) which skims the surface of feed zone liquid level 116 and oxidizing zone liquid level 118. The slag comprises largely CaCl 2 . Example VIII Invention with Fischer-Tropsch Synthesis As shown in Figure 3, Example I is continued and some of the carbon monoxide produced is mixed with steam 66 reacted to produce CO, + H 2 in water-gas shift reactor 60. The carbon dioxide is separated from hydrogen in C0 2 removal closed vessel 102. This hydrogen and hydrogen from H 2 outlet 130 are mixed with the remaining CO. Then the syngas 62 is reacted in Fisher-Tropsch reactor 64 to produce Fisher-Tropsch liquids 68. The Fischer-Tropsch liquids comprise naphtha, kerosene, and diesel fuel. By varying conditions of the Fischer-Tropsch process according to well-known techniques, the product distribution may be varied to favor naphtha or diesel, at will. Example IX Invention with Fischer-Tropsch and Boudouard When the process of Example VI is repeated, the CO, by-product from water-gas shift reactor 60 is fed to zone 106; it reacts with carbon dissolved in the molten metal to form two moles of CO for each mole of C0 2 fed to zone 106. MODIFICATIONS Specific compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variations of these compositions, methods, or embodiments are readily apparent to a person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein. Reference made above to any other specification or literature is intended to result in such patents or literature being expressly incorporated herein by reference. What is claimed is: TABLE A (Tonnes/Hour) Molten Metal Methanol by Example Feed, 105 Oxygen, 107 H 2 , 130 CO, 132 Circulation, 108 F-T Prod I SDA 22.3 25.0 1.75 43.8 9,000 25.9 II Methane 50 6.4 87.5 18,000 67.3 *24.2 III Steam *16.3 10.2 3.5 43.3 9,000 35.0 IV C() 2 + 39.8 10.6 1.75 69.1 9,000 35.6 * plus same SDA as in Example I

Claims: CLAIMS 1. In a process for decomposing carbon- and hydrogen-containing materials in a molten bath, the improvement comprising in combination providing a carbon monoxide stream comprising CO, oxidizing a portion of said CO to C0 2 , injecting at least a portion of said CO, into said molten metal at a point where said molten metal contains substantial quantities of dissolved carbon, whereby said dissolved carbon reacts with said C0 2 to form approximately two moles of CO for each mole of CO,. 2. A process according to Claim 1 wherein a portion of said CO produced is oxidized back to CO, which is recycled to react with additional amounts of carbon dissolved in the metal bath, providing a cooling means for adjusting temperature of said bath. 3. In a process for decomposing carbon- and hydrogen- containing feed materials in a molten bath, the improvement comprising in combination injecting said feed materials substantially downwardly into said bath under sufficient pressure as to penetrate through the bath and cause mixing of said feed materials with said molten metal. 4. A process according to Claim 3 wherein said feed materials are injected through a nozzle located below the surface of said bath. 5. A process according to Claim 3 wherein said feed materials are injected through a substantially downwardly directed conduit passing through an upper portion of a vessel containing said molten bath and communicating with a nozzle directed toward the surface of said bath, so that a jet of said material penetrates said bath for a distance of about 3-100 cm ( 1-36 inches) and causing mixing of the feed materials with the bath, and wherein said conduit is insulated or cooled to reduce the increase in temperature of said material as it flows through said conduit and said nozzle toward said molten bath. 6. A process according to Claim 3 wherein said conduit is substantially jacketed and cooling media flows through said jacket so as to substantially cool said conduit and the material flowing therein. 7. A process according to Claim 6 wherein said jacket is substantially annular with said conduit. 8. A process according to Claim 7 wherein the cooling media flowing through said jacket is itself discharged so as to substantially surround the jet of feed material exiting from said nozzle and is directed toward said surface of said molten bath. 9. A process according to Claim 3 wherein said feed material flows at a sufficient velocity to prevent the temperature in the annular space from exceeding about 315°C (about 600 °F). 10. A process according to Claim 3 wherein the velocity of the feed material leaving the nozzle is in the range of from about 30-300 meters per second (about 100-1000 feet per second). 1 1 . A process according to Claim 3 wherein the feed material is substantially in the gas phase as it exits said nozzle, and wherein said velocity of said feed material exiting the nozzle is sufficient to pierce the surface of said molten bath and cause bubbles to form within said molten bath. 12. A process according to Claim 3 wherein the pressure drop across said nozzle is at least about 200 psi and the liquid velocity is at least about 50 meters ( 150 feet) per second. 13. A process according to Claim 3 wherein the molten bath comprises iron and the feed material comprises hydrocarbons. 14. An apparatus for decomposing carbon- and hydrocarbon- containing feed materials in a molten bath, said apparatus comprising in combination: a. a closed vessel comprising sides, top, bottom and ends, and hermetically enclosing a two-phase bath comprising a liquid phase and a gas phase over said liquid phase: b. a molten bath contained within said vessel under said gas phase; c. a lance comprising downwardly directed conduit passing through an upper portion of said vessel and communicating with a nozzle directed toward the surface of said bath: d. • insulation means substantially surrounding the conduit to reduce the increase in temperature of said feed material as it flows through said conduit; e. a source of carbon- and hydrogen-containing feed material communicating with said conduit under sufficient pressure to force said feed material through said conduit and out through said nozzle into said vapor phase so as to be directed toward the surface of said bath; whereby a jet of said material penetrates through said bath, a distance of about 3-100 cm (1-36 inches) and causes mixing of the feed materials with the bath. 15. An apparatus according to Claim 14 wherein said conduit is substantially jacketed and cooling media flows through said jacket so as to substantially cool said conduit and the material flowing therein. 16. An apparatus according to Claim 14 wherein said jacket is substantially annular with said conduit. 17. An apparatus according to Claim 16 wherein the cooling media flowing through said jacket is itself discharged so as to substantially surround the jet of feed material exiting from said nozzle and directed through said molten bath. 18. An apparatus according to Claim 14 wherein said diameter of said conduit is sufficiently small that said feed material flows at a sufficient velocity of 1-10 meters/second, to prevent the temperature in said conduit from exceeding about 315°C (about 600 °F), and the total residence time of said feed material in said conduit is from about 0.1 to 10 seconds. 19. An apparatus according to Claim 18 wherein the velocity of the feed leaving the nozzle is in the range of about 30-300 meters per second (about 100-1,000 feet per second). 20. An apparatus according to Claim 3 wherein said feed material is substantially in the gas phase as it exits said nozzle, and wherein said velocity is the velocity of said feed material exiting the nozzle, and wherein the velocity of said feed material exiting the nozzle is sufficient to pierce through said molten bath about 3-100 cm (1-36 inches) and cause bubbles to form within said molten bath. 21. An apparatus according to Claim 14 wherein said lance comprises a conduit comprising tantalum or other refractory metal or Inconel™ 625 or other superalloy, said insulation comprises magnesium oxide, aluminum oxide, or spinels, said jacket comprises silicon nitride, alumina or boron nitride, and said coolant materials flowing through the annular space comprise argon, steam or methane. 22. A molten metal bath apparatus for decomposing carbon- and hydrogen-containing feed materials, comprising in combination: a. a feed zone for receiving said materials and dissolving said carbon; b. an oxidizing zone for receiving an oxygen-containing stream; c. a gas-impermeable vessel enclosing said bath and a gas- phase above said bath; d. baffle means mounted within said vessel and separating gas-phase of said feed zone from the gas-phase of said oxidizing zone; e. said first baffle means extending substantially gas tight downward from said top wall of said vessel and having a lower edge entering, but not extending through, said molten metal bath, and defining said gas phases of said feed zone and said oxidizing zone; f. feed means comprising a substantially downwardly directed conduit passing through an upper portion of a vessel containing said molten bath and communicating with a nozzle directed toward said bath, so that a jet of said material penetrates said bath causing mixing of the feed materials with the bath, and wherein said conduit is insulated or cooled to reduce the increase in temperature of said material as it flows through said conduit and said nozzle toward said molten bath. 23. . A process according to Claim 22 wherein said feed materials are injected through a nozzle directed substantially downwardly through said molten bath. 24. A process according to Claim 22 wherein said feed materials are injected through a substantially downwardly directed conduit passing through the wall of a vessel containing said molten bath and communicating with a nozzle directed toward the surface of said bath so that a jet of said material strikes the surface of said bath, depressing the surface and causing mixing of the materials with the bath, and wherein said conduit is insulated or cooled to reduce the increase in temperature of said material as it flows through said conduit and said nozzle. 25. A process according to Claim 22 wherein said conduit is jacketed and the cooling media flows through said jacket so as to substantially cool said conduit and the material flowing therein. 26. A process according to Claim 25 wherein said jacket is substantially annular with said conduit. 27. A process according to Claim 26 wherein the feed material flowing through said jacket is itself discharged so as to substantially surround the feed material exiting from said nozzle and directed toward said surface of said molten bath. 28. A molten metal bath apparatus for decomposing carbon- and hydrogen-containing feed and producing hydrogen, said apparatus comprising: a gas-impermeable vessel having a top wall and a bottom wall, means for feeding said carbon- and hydrogen-containing feed to said vessel, a molten metal bath within a bottom of said vessel, said molten metal bath being spaced from said top wall, means including said vessel for defining a feed zone within said vessel for receiving said feed and dissolving said carbon and an oxidizing zone within said vessel for receiving materials containing oxygen, a gas-phase in each said zone above the level of said molten metal bath and between the molten metal bath and the top wall of said vessel, the improvement wherein said means defining said feed zone and said oxidizing zone comprises: a. first baffle means mounted within said vessel separating a gas-phase of said feed zone from a gas-phase of said oxidizing zone, said first baffle means extending substantially gas tight downward from said top wall of said vessel and having a lower edge entering, but not extending through, said molten metal bath, so as to separately define said gas-phases of said feed zone and said oxidizing zone; b. second baffle means mounted within said vessel, spaced from said first baffle means and within said bath, having a downward extension including an upper edge at a level higher than said lower edge of said first baffle means and having an integral, horizontal extension extending substantially horizontally from a lower end of said downward extension and being of a length so as to extend beyond and below the lower edge of said first baffle means, whereby said integral, horizontal extension defines with the bottom wall of said gas-impermeable vessel a lower 5 circulation zone for said molten bath from said feed zone to said oxidizing zone, said first baffle means and said downward extension of said second baffle means partially defines said feed zone and said oxidizing zone, said downward extension and said integral horizontal extension 10 of said second baffle means and said first baffle means define a generally L-shaped recycling zone, whereby molten material from said feed zone containing carbon from said feed may circulate under said horizontal extension of the second baffle means into said oxidizing 15 zone, and wherein liquid from said oxidizing zone, lowered in carbon after contact with oxygen, may flow reversely above the horizontal extension of the second baffle means beneath the lower edge of the first baffle means and rise upwardly between the downward extension of said second 20 baffle means and said first baffle means and over the upper edge of the second baffle means downward extension in a continuous circulation loop back into said feed zone; and c. said means for feeding said carbon- and hydrogen- 25 containing feed to said vessel comprises a substantially downwardly directed conduit passing through an upper portion of said gas-impermeable vessel containing said molten bath, said conduit communicating with a nozzle directed toward the surface of said bath, so that a jet of said feed material strikes the surface of said bath, depressing the surface and causing mixing of the feed materials with the 5 bath, and wherein said conduit is insulated or cooled to reduce the increase in temperature of said material as it flows through said conduit and said nozzle toward said molten bath.

Inventors: MALONE DONALD P, MILLER CHARLES B, WISEMAN JONATHAN A, MALONE, DONALD, P., MILLER, CHARLES, B., WISEMAN, JONATHAN, A.
Applicants: ASHLAND OIL INC, ASHLAND OIL, INC.
Application year: 1994
Main classification: C10J3
IPC codes: C10J3